CN108083725B - Polymer modified cement-based composite board and preparation method thereof - Google Patents
Polymer modified cement-based composite board and preparation method thereof Download PDFInfo
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- CN108083725B CN108083725B CN201711363700.7A CN201711363700A CN108083725B CN 108083725 B CN108083725 B CN 108083725B CN 201711363700 A CN201711363700 A CN 201711363700A CN 108083725 B CN108083725 B CN 108083725B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/02—Selection of the hardening environment
- C04B40/024—Steam hardening, e.g. in an autoclave
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
- C04B2201/52—High compression strength concretes, i.e. with a compression strength higher than about 55 N/mm2, e.g. reactive powder concrete [RPC]
Abstract
The invention discloses a polymer modified cement-based composite board and a preparation method thereof; the raw materials comprise: aggregate, cement, inorganic aggregate, a high-molecular mixture, a cement composite additive, citrate, a defoaming agent and a certain mass of water. The weight parts of the raw materials are as follows: 16-29 parts of aggregate, 13-25 parts of cement, 28.4-49 parts of inorganic powder, 2-5 parts of a high polymer mixture, 12.6 parts of a cement composite additive, 0.2-0.5 part of citrate, 0.05-0.1 part of a defoaming agent and the balance of water; the manufacturing process of the composite board comprises the following steps: stirring the mixture for a certain time by using cement, inorganic aggregate, a high-molecular mixture, a cement composite additive, a small amount of defoaming agent and water, then adding aggregate, citrate, the rest defoaming agent and water, uniformly stirring, grouting for forming, demolding, drying, fixing thickness, polishing and autoclaving to obtain the composite board. The invention has the advantages of simple forming process, stable property, wide application range, high compressive and flexural strength, low water absorption and the like.
Description
Technical Field
The invention relates to a composite board and a preparation method thereof, belongs to the technical field of composite boards prepared from high molecular polymers, and particularly relates to a polymer modified cement-based composite board and a preparation method thereof.
Background
Artificial stone is a new type of decorative material developed in the 60's of the 20 th century. The artificial stone includes inorganic artificial stone and organic artificial stone according to different cementing materials. But the existing artificial stones have the defects which are difficult to overcome: the characteristics of the cementing material (unsaturated resin and acrylic resin) of the organic artificial stone are that the inorganic artificial stone is easy to age and deteriorate and is not fireproof under the conditions of ultraviolet irradiation, acid and alkali corrosion, dry and wet cycle and the like, the application range of the inorganic artificial stone is greatly limited, the inorganic artificial stone has the advantages of good durability, good fire resistance and the like, and can be applied to decoration with high fireproof grade requirements of external walls, families and the like, but because the defects of high water absorption, poor mechanical property, low glossiness, poor decoration effect and the like of the traditional inorganic artificial stone such as terrazzo, the traditional cement-based artificial stone and the like exist, the decoration design requirements are difficult to meet, and the market application of the traditional inorganic artificial stone is few.
The cement base plate material is used as a synthetic artificial stone, is between a gypsum board and a stone material, is greatly superior to the gypsum board in physical and mechanical properties, and has a price far lower than that of the stone material, so that the cement base plate material becomes a building material widely used in the building industry; however, the traditional cement-based plate also has the defects that the artificial stone is difficult to overcome: for example, a large amount of organic glue or unsaturated resin is added as a cementing material, so that the product tends to be organic artificial stone, and the product performance (color, texture, fire-proof grade and the like) after the polymer is modified is not ideal and cannot meet the actual production and use requirements; the cement is used as a single cementing material in a large amount, the product property of the cement is similar to that of terrazzo inorganic artificial stones, and the water absorption rate, the physical and mechanical properties and the human body sense of the product greatly limit the application range of the cement.
Adding a certain amount of high molecular polymer into a cement-based plate is an important way to overcome a series of defects and improve performance, and a certain achievement is achieved in the research of polymer composite plates at present. For example, Wang gao et al, Zhangzhou Hongyu science and technology development Limited, published patent (publication No. CN104926982A), which utilizes polymers such as acrylic acid or acrylic ester, and then adds silane coupling agent, polyvinyl alcohol, ammonium persulfate and other initiators to jointly act to obtain the composite board. The patent (publication number: CN107226637A) discloses a novel artificial quartz stone plate and a manufacturing method thereof, wherein structural members are inserted into a fire-resistant layer and a grid layer which are arranged in the artificial quartz stone plate, quartz stone crystals and auxiliary materials are manufactured by using a vacuum condition through an isomeric polymerization technology, but the manufacturing process of the plate is complex, and the damage of the structural members and the grid layer caused by the later polishing and thickness setting of the plate can reduce the application range and the service life of the product. The invention discloses a cement-based artificial stone and a production process thereof (publication number: CN101913806A), which is prepared by mixing cement and crushed stone into a gelling system, adding a water reducing agent, high-efficiency active powder and the like to improve the fluidity and the reaction rate of the cement, removing bubbles and compacting a plate body through vacuum high pressure to obtain the cement-based artificial stone with excellent performance, but the product knowledge simply utilizes the cement which is a single gelling system, and the problems of the mechanical property, the water absorption rate and the like of the product are not substantially improved.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a polymer modified cement-based composite board, and the obtained composite board has the advantages of quick forming, simple process, wide application range, high compressive and flexural strength, low water absorption and the like.
The invention also aims to provide a preparation method of the polymer modified cement-based composite board.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a polymer modified cement-based composite board which is prepared from the following raw materials in parts by weight: 16-29 parts of aggregate, 13-25 parts of cement, 28.5-49 parts of inorganic aggregate, 2-5 parts of a high polymer mixture, 12.6 parts of a cement composite additive, 0.2-0.5 part of citrate, 0.05-0.1 part of a defoaming agent and the balance of water.
Further, the grading of the aggregate adopts: 2-5 parts of less than or equal to 10 meshes, 8-16 parts of 10-20 meshes and 6-8 parts of 20-40 meshes; the aggregate is quartz sand, granite, feldspar, iron tailings, river sand, amphibole and other single or multiple mixtures, and SiO in the aggregate2The content of the components is more than or equal to 75 percent.
Further, the cement type is one or more of ordinary portland cement, composite portland cement or fly ash portland cement; the cement strength grade adopts one or more of the following labels of 32.5R, 42.5R, 52.5 and 52.5R; SO in cement3Less than or equal to 3.5 percent, initial setting time of not less than 45min, final setting time of not more than 9h and water cement ratio of cement paste0.4-0.45 is adopted.
Further, the inorganic aggregate comprises the following raw materials in parts by weight: SiO 2217-30 parts of CaO 9-14 parts of CaCO32-4 parts of MgO and 0.4-1 part of MgO; SiO removal2The grain diameter of the other aggregates is less than or equal to 0.074 mm;
wherein SiO is2The powder comprises 7-9 parts of 40-80 meshes, 4-7 parts of 80-120 meshes and 6-14 parts of more than 325 meshes; SiO 22The powder is obtained by high-temperature calcination at 573 ℃ and heat preservation for 1 hour, and the detection of active ingredients is more than or equal to 85 percent.
Further, the high polymer mixture is a mixture of alkali-soluble styrene-acrylic resin and stearic acid, the stearic acid can be replaced by ammonium stearate, the alkali-soluble styrene-acrylic resin can be replaced by alkali-soluble styrene-acrylic resin with an acid value of more than 200, a molecular weight Mn of 3000-6000, a molecular weight distribution of less than 2 and a glass transition temperature of more than 100 ℃; the preparation method comprises the following steps:
stearic acid provided by Hangzhou grease chemical industry Co., Ltd and alkali-soluble styrene-acrylic resin provided by megaly chemical industry (hong Kong) Co., Ltd are adopted;
the mixing process comprises the following steps: adding 40 wt% (based on the weight of the total powder) of diethylene glycol dimethyl ether and 60 wt% (based on the weight of the total powder) of deionized water into a reaction kettle, stirring at 200rpm for 10min, adding stearic acid powder and alkali-soluble styrene-acrylic resin powder in a multi-point feeding manner (the weight ratio of stearic acid to alkali-soluble styrene-acrylic resin is 50: 50-80: 20), heating to 80-90 ℃, preheating and stirring for 30min, stopping stirring, continuously heating to 160 ℃, keeping the temperature for 2-3 h until the solvent is completely evaporated, grinding the residue through a 200-mesh screen, and collecting fine powder, namely uniformly dispersed polymer mixture dry powder.
Further, the cement composite admixture is prepared by mixing 2 parts by weight of SM type water reducing agent, 0.6 part by weight of accelerator (862 type or 8604 type), 2 parts by weight of thickener (tt935, tt936, Y203 and PAE) and 8 parts by weight of polyvinyl alcohol (medium viscosity, molecular weight less than 130000) under the condition of water bath; the preparation method comprises the following steps:
adding 60 wt% (based on the total weight of the additive solution) of deionized water into an electromagnetic stirring pot, adding polyvinyl alcohol, an accelerator and a thickener when heating in a water bath to 45 ℃, continuously stirring for 6h (+ -10 min) under the condition of 400rpm, adding a water reducing agent when measuring the pH value between 3.6 and 3.8, continuously heating to 50 ℃, keeping the stirring speed unchanged, stirring for 1h (+ -15 min), immediately stopping heating when measuring the pH value between 2.1 and 2.2 and the viscosity between 130 and 160 mPa.s at the test temperature of 40 ℃, and quickly cooling to obtain the cement composite additive.
Further, the solid content of the prepared cement composite additive is more than or equal to 50 percent.
Further, the defoaming agent can be emulsified silicone oil, polyoxyethylene polyoxypropylene pentaerythritol ether or polyoxypropylene glycerol ether.
On the other hand, the invention provides a preparation method of the polymer modified cement-based composite board, which comprises the following steps:
1) respectively dividing the aggregates with different meshes, the cement and the inorganic aggregates into two groups, respectively extracting the aggregates into a mixer according to the formula by a bucket elevator, uniformly mixing the aggregates and the cement, and then conveying the aggregates to two storage towers for later use;
2) during production, cement and inorganic aggregate mixture is conveyed into a stirring pot through a belt conveyer, a high-molecular mixture, a cement composite additive, a part of defoaming agent and a certain mass of water are added and stirred for 20-30 min, aggregate, citrate and the rest of defoaming agent are added and stirred for 10-15 min to be uniform, and then the mixture is injected into a mold for molding;
3) and demolding the blank, naturally drying, polishing by fixed thickness, conveying to an autoclave curing box for reaction and curing, and naturally curing after curing to obtain the composite board.
Further, dripping the defoaming agent in the step 2) for two times, wherein the dripping amount is determined according to the actual temperature, dripping 4-5 drops when the temperature T is less than or equal to 25 ℃, dripping 5-6 drops when the temperature T is less than or equal to 26 ℃ and less than or equal to 35 ℃, and dripping 7 drops or more when the temperature T is more than or equal to 36 ℃;
further, polishing the blank in the step 3) to a fixed thickness, conveying the blank to an autoclaved curing chamber, introducing steam with the steam pressure of 0.8-1 MPa and the steam temperature of 160-180 ℃, curing, and curingThe curing time is 7-8 h, and the packaging and delivery can be realized after curing is completed and curing is carried out for 7d at normal temperature; the high-temperature steam is recycled and calcined SiO through a circulating water system2The heat dissipated later is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1) the polymer modified cement-based composite board is prepared by stirring cement, inorganic aggregate, a high-molecular mixture, a cement composite additive, a small amount of defoaming agent and water for a certain time, then adding aggregate, citrate, the rest defoaming agent and water, uniformly stirring, then performing grouting forming, demolding, drying, thickening, polishing and autoclaving maintenance, and the polymer modified cement-based composite board has the advantages of rapid forming, simple process, wide application range, high compressive and flexural strength, low water absorption rate and the like.
2) The invention combines the physical aspect of high molecular polymer and the chemical aspect of inorganic material under the condition of autoclaving to form a composite gel system on the basis that the aggregate and the powder form a close packing state, thereby reducing the water absorption of the plate and improving the integral compactness, thereby greatly enhancing the physical mechanical property and the surface wear resistance of the plate.
Detailed Description
The invention discloses a polymer modified cement-based composite board and a preparation method thereof. The polymer modified cement-based composite board comprises the following raw materials in percentage by weight:
16-29% of aggregate, 13-25% of cement, 28.4-49% of inorganic aggregate, 2-5% of polymer mixture, 12.6% of cement composite additive, 0.2-0.5% of citrate, 0.05-0.1% of defoaming agent and the balance of water.
The preparation method of the polymer modified cement-based composite board comprises the following steps:
1) respectively extracting cement and inorganic aggregates by using a fighter elevator according to a formula, conveying aggregates with different grades to a mixer for uniform mixing, and then conveying the aggregates to two storage towers; the cement strength grade adopts one or more of the following labels of 32.5R, 42.5R, 52.5 and 52.5R;
2) during production, unloading raw materials according to a formula through a discharge valve, conveying the raw materials into a stirring pot through a belt conveyer, adding the prepared high polymer mixture, the cement composite admixture, a small amount of defoaming agent (3-5 drops) and a certain mass of water, stirring for 20-30 min, adding aggregate, citrate and the rest defoaming agent (1-2 drops), stirring for 10-15 min until the mixture is uniform, and injecting the mixture into a mold for molding;
3) and (3) demoulding the blank, naturally drying for 24-48 h, polishing to a fixed thickness, naturally drying for 24-48 h, conveying to an autoclaved curing box, setting the steam temperature to be 160-180 ℃ and the steam pressure to be 0.8-1 MPa, curing for 7-8 h, curing at room temperature for 7d to obtain a plate, and leaving the factory after subsequent procedures such as art designing, packaging workshops and the like.
In order to solve the problem that the properties of a product modified by a single gelling system and a polymer in a cement-based plate are not ideal, the technical principle and measures adopted by the invention are as follows:
firstly, aggregate and powder in continuous gradation are adopted.
Calculating to obtain the continuous gradation and the adding amount of the aggregate and the powder, so that the stacking forms of the aggregate and the powder in the plate are similar to or close to the closest stacking form: on one hand, the product gap is reduced, and on the other hand, the consumption of other cementing materials such as high molecular polymer and cement can be reduced, thereby not only being green and environment-friendly, but also reducing the production cost.
And the skeleton effect and the stress transmission effect of the aggregate also provide higher physical strength for a cement gelling system.
Secondly, high molecular polymer is adopted as an additive. The high molecular polymer selects a mixed system of stearic acid and alkali-soluble styrene-acrylic acid and a prepared cement composite additive.
A mixed system of stearic acid and alkali-soluble styrene-acrylic acid is adopted: the system can be dispersed into an crosslinked network structure after being dissolved in the system, is quick in air hardening, can have high strength in the early stage with a plate blank by double gluing and hardening effects in the early stage of forming with cement, and has the characteristic of high temperature resistance, so that the plate blank can embody good heat resistance and stability in the later stage of autoclaved curing; meanwhile, after moisture of the dispersed particles is completely hydrated or dried to lose, the dispersed particles can be coated on the surfaces of the outer walls of cement and other aggregates to form a good waterproof protective layer, so that capillary channels through which the moisture passes in the crystal structure are blocked, and the effects of improving the compactness and waterproofness of a cement product are achieved.
The cement composite additive is prepared from water reducing agent, accelerating agent, thickening agent and polyvinyl alcohol. The water reducing agent can well improve the dispersibility of the cement and increase the specific surface area of cement hydration by controlling the content, so that the hydration rate of the cement in the stirring process is improved; the addition of a certain amount of thickening agent can improve the emulsifying and dispersing performance of high molecular substances and can also improve the dispersibility and hydration rate of cement paste; more importantly, the high molecular polymers can lead the cement gelling system to have the characteristic of higher fluidity; in addition, in the hydration process, the polymer gradually forms a polymer film or is aggregated into particles, the polymer film can be uniformly dispersed along with water, and the particles can cover the surface of cement gel or fill capillary pores of cement hydrate after the water is completely hydrated or dried and lost in the later period; the quantity of harmful holes in the plate is greatly reduced through the blocking and burying effects, and the communication of the holes in the plate is blocked in a large range, so that the capillary pore structure of the hardened slurry is improved, and the aims of reducing the porosity and water absorption of the plate are fulfilled.
After the high molecular polymer is added, a high molecular film or particle formed after dispersion or polymerization can gradually cover ettringite generated by cement hydration after water is completely hydrated or dried and lost; the ettringite is in a strip shape or a needle shape and is easy to grow in a staggered way, when a polymer film or particles are covered on the surface or filled in pores formed by the ettringite, the damage difficulty of the ettringite is greatly increased, and macroscopically, the physical mechanical property of the plate is greatly improved; the flexibility and the bending strength of the cement matrix can be increased by the polymer and the reticular membrane structure formed after stirring and dispersing; the addition of various organic assistants can raise the dispersivity of cement grains in slurry, increase the contact area between cement grains and water and raise the performance of the product greatly.
Thirdly, adopting an autoclaved curing means.
By adding a certain amount of inorganic aggregate (CaO, SiO)2、CaCO3And MgO) which generates C-S-H (calcium silicate hydrate) by a hydrothermal reaction between a calcareous material and a siliceous material in an autoclave curing environment.
CaO, cement and SiO2The powder is dispersed in the gaps and pores of the aggregate, and CaO and cement are gradually dissolved in a high-temperature high-pressure hydrothermal environment and are mixed with SiO in an alkaline environment2C-S-H is generated through reaction, most of the C-S-H is in a gel state, on one hand, the gel can form a buffer layer and a cross-linking layer between large particles, on the other hand, the loose and porous gel can be filled in pores to play the roles of blocking and sponge; meanwhile, a small part of C-S-H with better crystallization can be converted into tobermorite, and the physical mechanical property and compactness of the plate can be improved in both aspects.
In addition, the reaction of the calcium-silicon system to generate C-S-H and the transformation of the C-S-H to tobermorite can be rapidly promoted in an autoclaved curing environment after the MgO is hydrated, and meanwhile, the cement contains a certain amount of C4AF(4CaO·Al2O3·Fe2O3) And C3A(3CaO·Al2O3) The reaction is inhibited during hydration, and MgO added is preferentially mixed with Al2O3Reacting to form fine-grained magnalium garnet with stable properties3The inorganic gel network is formed by filling the inorganic gel network in a gel system to play a role in stress transfer, so that on one hand, the surrounding cement hydration products and quartz sand are tightly combined, and on the other hand, the generated C-S-H in different forms can cover the surface of large particles to prevent water molecules from entering and can also block the rest gaps and capillary channels.
The invention combines the physical aspect of high molecular polymer and the chemical aspect of inorganic material under the condition of autoclaving to form a composite gel system on the basis that the aggregate and the powder form a close packing state, thereby reducing the water absorption of the plate and improving the integral compactness, thereby greatly enhancing the physical mechanical property and the surface wear resistance of the plate.
The invention of the present application is further illustrated below with reference to examples, which should not be construed as limiting the claims.
The following units of parts by weight of the raw materials can be g or kg:
example 1
The polymer modified cement-based composite board comprises the following components in parts by weight:
16 parts of bone particles (2 parts of less than or equal to 10 meshes, 8 parts of 20-20 meshes, 6 parts of 20-40 meshes), 42.95 parts of inorganic aggregate (10 parts of CaO, 2 parts of CaCO)30.95 parts of MgO, SiO2Powder lot: 9 parts of 40-80 meshes, 7 parts of 80-120 meshes and 14 parts of more than or equal to 325 meshes), 25 parts of cement (common Portland cement marked by the number 42.5), 3 parts of a high-molecular mixture (adopting a mixed system of ammonium stearate and alkali-soluble styrene-acrylic acid), 12.6 parts of a cement composite additive (with the solid content of 50%), 0.4 part of sodium citrate and 0.05 part of a defoaming agent (emulsified silicone oil), wherein the water-cement ratio of the slurry is 0.4, and the water addition amount is 8.4 parts of water.
The preparation method of the mixed system of the amine stearate and the alkali-soluble styrene-acrylic acid comprises the following steps:
adding 40 wt% (based on the weight of the total powder) of diethylene glycol dimethyl ether and 60 wt% (based on the weight of the total powder) of deionized water into a reaction kettle, stirring at 200rpm for 10min, adding stearic acid powder and alkali-soluble styrene-acrylic resin powder in a multi-point feeding mode (the weight ratio of stearic acid to alkali-soluble styrene-acrylic resin is 50:50), heating to 80 ℃, preheating and stirring for 30min, stopping stirring, continuously heating to 160 ℃, keeping the temperature for 134min, completely evaporating the solvent, grinding the residue through a 200-mesh screen, and collecting fine powder, namely uniformly dispersed polymer mixture dry powder.
The cement composite additive is prepared by mixing 2 parts by weight of SM type water reducing agent, 0.6 part by weight of accelerator 8604, 2 parts by weight of thickener tt936 and 8 parts by weight of polyvinyl alcohol under the condition of water bath; the preparation method of the cement composite admixture comprises the following steps:
adding 60 wt% (based on the total weight of the additive solution) of deionized water into an electromagnetic stirring pot, heating in a water bath to 45 ℃, adding polyvinyl alcohol, an accelerator and a thickener, continuously stirring for 6h under the condition of 400rpm, adding a water reducing agent when the pH value is measured to be 3.8, continuously heating to 50 ℃, keeping the stirring speed unchanged, stirring for 1h, immediately stopping heating when the pH value is measured to be 2.2 and the viscosity is 160mPa & s, and quickly cooling to obtain the cement composite additive.
The preparation process of the polymer modified cement-based composite board comprises the following steps:
(1) discharging mixed powder of 25 parts of cement and 42.95 parts of inorganic aggregate from a storage tower according to a formula, conveying the mixed powder to a stirring pot through a belt, adding 3 parts of macromolecular mixture and 12.6 parts of cement composite additive, adding 4 drops of defoaming agent and 6.4 parts of water, and stirring for 20 min;
(2) adding 16 parts of bone particles, the rest 2 drops of defoaming agent and 2 parts of water into a stirring pot, stirring for 10min until the mixture is uniform, and injecting the mixture into a mold for molding;
(3) naturally drying the molded and demoulded blank for 36h in a room temperature environment, and naturally drying for 36h after passing through a thickness-fixing and polishing production line to obtain a semi-finished product;
(4) then conveying the semi-finished product into an autoclave curing box, setting the steam temperature to be 180 ℃, the steam pressure to be 1MPa, and curing time to be 7 h;
(5) and taking out after the maintenance is finished, and naturally maintaining for 7d to obtain the finished product.
The prepared composite board is detected according to national standards JC/T908-2013, GB/T18601-2009 and GB8624-2006, and the average value of the compressive strength is 113.7MPa, the bending strength is 19MPa and the wear resistance is 5.3g/cm through a compressive and flexural load test2The Mohs hardness is 6, the water absorption rate is 0.09 h, the mirror surface glossiness is 75, the fire-retardant rating A1 is shown in Table 1.
Example 2
The polymer modified cement-based composite board comprises the following components in parts by weight:
21 parts of 5 parts of bone particles which are less than or equal to 10 meshes, 10 parts of 20-20 meshes, 6 parts of 20-40 meshes), 49 parts of inorganic aggregate (14 parts of CaO, 4 parts of CaCO)31 part of MgO, SiO2Powder lot: 9 parts of 40-80 meshes, 7 parts of 80-120 meshes and 14 parts of more than or equal to 325 meshes), 13 parts of cement (fly ash portland cement with the label of 42.5R), and 4 parts of high polymer mixture (prepared by adoptingA composite system of modified stearic acid and alkali-soluble styrene-acrylic acid), 12.6 parts of a cement composite admixture (solid content is 53%), 0.3 part of sodium citrate, 0.1 part of a defoaming agent (polyoxyethylene polyoxypropylene pentaerythritol ether), 0.45 part of water-cement ratio of slurry and 6.6 parts of water.
The preparation method of the mixed system of stearic acid and alkali-soluble phenethyl-allyl acid comprises the following steps:
adding 40 wt% (based on the weight of the total powder) of diethylene glycol dimethyl ether and 60 wt% (based on the weight of the total powder) of deionized water into a reaction kettle, stirring at 200rpm for 10min, adding stearic acid powder and alkali-soluble styrene-acrylic resin powder in a multi-point feeding mode (the weight ratio of stearic acid to alkali-soluble styrene-acrylic resin is 80:20), heating to 90 ℃, preheating and stirring for 30min, stopping stirring, continuously heating to 160 ℃, keeping the temperature for 177min until the solvent is completely evaporated, grinding the residue through a 200-mesh screen, and collecting fine powder, namely uniformly dispersed polymer mixture dry powder.
The cement composite additive is prepared by mixing 2 parts by weight of SM type water reducing agent, 0.6 part by weight of accelerator 862, 2 parts by weight of thickener Y203 and 8 parts by weight of polyvinyl alcohol under the condition of water bath; the preparation method of the cement composite admixture comprises the following steps:
adding 60 wt% (based on the total weight of the additive solution) of deionized water into an electromagnetic stirring pot, adding polyvinyl alcohol, an accelerator and a thickener when heating in a water bath to 45 ℃, continuously stirring for 6h under the condition of 400rpm, adding a water reducing agent when measuring the pH value to be 3.6, continuously heating to 50 ℃, keeping the stirring speed unchanged, stirring for 1h, immediately stopping heating when measuring the pH value to be 2.1 and the viscosity to be 130mPa & s, and quickly cooling to obtain the cement composite additive.
The preparation process of the polymer modified cement-based composite board comprises the following steps:
(1) discharging mixed powder of 13 parts of cement and 49 parts of inorganic aggregate from a storage tower according to the formula, conveying the mixed powder to a stirring pot through a belt, adding 4 parts of macromolecular mixture and 12.6 parts of cement composite additive, adding 5 drops of defoaming agent and 5.6 parts of water, and stirring for 25 min;
(2) adding 21 parts of bone particles, the rest 1 drop of defoaming agent and 1 part of water into a stirring pot, stirring for 15min until the mixture is uniform, and injecting the mixture into a mold for molding;
(3) naturally drying the molded and demoulded blank for 24 hours in a room temperature environment, and naturally drying for 24 hours after passing through a thickness-fixing and polishing production line to obtain a semi-finished product;
(4) then conveying the semi-finished product into an autoclave curing box, setting the steam temperature to be 160 ℃, the steam pressure to be 0.8MPa, and curing for 8 h;
(5) and naturally curing for 7d after curing is finished to obtain a finished product.
The prepared composite board is detected according to national standards JC/T908-2013, GB/T18601-2009 and GB8624-2006, and the average value of the compressive strength, the bending strength and the wear resistance of the prepared composite board are 104.2MPa, 24MPa and 6.8g/cm respectively through a compressive and flexural load test2The Mohs hardness is 6, the water absorption is 0.14 h, the specular gloss is 80, and the fire resistance is A1, and the properties are detailed in Table 1.
Example 3
The polymer modified cement-based composite board comprises the following components in parts by weight:
29 parts of bone particles (5 parts of less than or equal to 10 meshes, 16 parts of 20-20 meshes, 8 parts of 20-40 meshes), 38.8 parts of inorganic aggregate (10 parts of CaO, 2 parts of CaCO)30.8 part of MgO, SiO2Powder lot: 8 parts of 40-80 meshes, 7 parts of 80-120 meshes and 11 parts of more than or equal to 325 meshes), 15 parts of cement (the composite Portland cement with the label of 42.5R), 4 parts of high molecular polymer (a stearic acid and alkali-soluble styrene-acrylic acid composite system), 12.6 parts of a cement composite additive (with the solid content of 51 percent), 0.5 part of sodium citrate and 0.1 part of a defoaming agent (polyoxypropylene glycerol ether), wherein the water-cement ratio of the slurry is 0.45, and the total amount of water is 5.3 parts of water.
The preparation method of the mixed system of stearic acid and alkali-soluble phenethyl-allyl acid comprises the following steps:
adding 40 wt% (based on the weight of the total powder) of diethylene glycol dimethyl ether and 60 wt% (based on the weight of the total powder) of deionized water into a reaction kettle, stirring at 200rpm for 10min, adding stearic acid powder and alkali-soluble styrene-acrylic resin powder in a multi-point feeding mode (the weight ratio of stearic acid to alkali-soluble styrene-acrylic resin is 60:40), heating to 85 ℃, preheating and stirring for 30min, stopping stirring, continuously heating to 160 ℃, keeping the temperature for 154min, allowing the solvent to completely evaporate, grinding the residue through a 200-mesh screen, and collecting fine powder.
The cement composite additive is prepared by mixing 2 parts by weight of SM type water reducing agent, 0.6 part by weight of accelerator 8604, 2 parts by weight of thickener PAE and 8 parts by weight of polyvinyl alcohol under the condition of water bath; the preparation method of the cement composite admixture comprises the following steps:
adding 60 wt% (based on the total weight of the additive solution) of deionized water into an electromagnetic stirring pot, adding polyvinyl alcohol, an accelerator and a thickener when heating in a water bath to 45 ℃, continuously stirring for 60min under the condition of 400rpm, adding a water reducing agent when measuring the pH value to be 3.6, continuously heating to 50 ℃, keeping the stirring speed unchanged, stirring for 1h, immediately stopping heating when measuring the pH value to be 2.1 and the viscosity to be 140mPa & s, and quickly cooling to obtain the cement composite additive.
The preparation process of the polymer modified cement-based composite board comprises the following steps:
(1) discharging mixed powder of 15 parts of cement and 38.8 parts of inorganic aggregate from a storage tower according to the formula, conveying the mixed powder to a stirring pot through a belt, adding 4 parts of high polymer mixture and 12.6 parts of cement composite additive, adding 4 drops of defoaming agent and 4.3 parts of water, and stirring for 30 min;
(2) adding 29 parts of bone particles, the rest 3 drops of defoaming agent and 1 part of water into a stirring pot, stirring for 15min until the mixture is uniform, and injecting the mixture into a mold for molding;
(3) naturally drying the molded and demoulded blank for 36h in a room temperature environment, and naturally drying for 24h after passing through a thickness-fixing and polishing production line to obtain a semi-finished product;
(4) then conveying the semi-finished product into an autoclave curing box, setting the steam temperature to be 180 ℃, the steam pressure to be 1MPa, and curing time to be 7 h;
(5) and taking out and drying after maintenance to obtain a finished product.
The contents of the effect test examples are as follows.
Examples of Effect test
Examples 1-3 composite boards made according to the national standards JC/T908-2013, GB/T18601-2009 and GB8624-2006 were tested for relevant properties, and the average of compressive strength was 117.6MPa, the flexural strength was 27MPa, and the abrasion resistance was 5.2g/cm2The Mohs hardness is 7, the mirror surface glossiness is 75, the fire-retardant rating is A, the water absorption rate is 0.16% within 48h, and the properties are detailed in Table 1.
TABLE 1 table of the properties of the finished product and reference table of the test standards
As can be seen from Table 1, the polymer modified cement-based composite boards prepared in the above examples 1 to 3 satisfy a series of excellent properties, and have significantly improved physical mechanical properties and water absorption, so that they have good market prospects.
The present invention is not limited to the above-described embodiments, and various changes and modifications of the present invention are intended to be included within the scope of the claims and the equivalent technology of the present invention if they do not depart from the spirit and scope of the present invention.
Claims (9)
1. The polymer modified cement-based composite board is characterized by being prepared from the following raw materials in parts by weight:
16-29 parts of aggregate;
13-25 parts of cement;
28.4-49 parts of inorganic aggregate;
2-5 parts of a polymer mixture;
12.6 parts of a cement composite additive;
0.2-0.5 part of citrate;
0.05-0.1 part of defoaming agent;
the balance of water;
the polymer mixture is a mixture of stearic acid or amine stearate and alkali-soluble styrene-acrylic resin; the alkali-soluble styrene-acrylic resin is an alkali-soluble styrene-acrylic resin with an acid value of more than 200, a molecular weight Mn of 3000-6000, a molecular weight distribution of less than 2 and a glass transition temperature of more than 100 ℃;
the mixing process comprises the following steps:
adding diethylene glycol dimethyl ether accounting for 40 wt% of the total powder and deionized water accounting for 60 wt% of the total powder into a reaction kettle, stirring for 10min at a stirring speed of 200rpm, adding stearic acid powder and alkali-soluble styrene-acrylic resin powder in a multi-point feeding mode, wherein the weight ratio of stearic acid to alkali-soluble styrene-acrylic resin is 50: 50-80: 20, heating to 80-90 ℃, preheating and stirring for 30min, stopping stirring, continuously heating to 160 ℃, keeping the temperature for 2-3 h, completely evaporating the solvent, grinding the residue through a 200-mesh screen, and collecting fine powder, namely uniformly dispersed high-molecular mixture dry powder.
2. The polymer-modified cement-based composite board as claimed in claim 1, wherein: the grading of the aggregate adopts: 2-5 parts of less than or equal to 10 meshes, 8-16 parts of 10-20 meshes and 6-8 parts of 20-40 meshes; the aggregate is quartz sand, granite, feldspar, iron tailings, river sand and amphibole which are mixed singly or in multiple, and SiO is contained in the aggregate2The content of the components is more than or equal to 75 percent.
3. The polymer-modified cement-based composite board as claimed in claim 1, wherein: the cement type is one or more of ordinary portland cement, composite portland cement or fly ash portland cement; SO in cement3Less than or equal to 3.5 percent, the initial setting time is not less than 45min, the final setting time is not more than 9h, and the water cement ratio of the cement paste is 0.4-0.45.
4. The polymer-modified cement-based composite board as claimed in claim 1, wherein: the inorganic aggregate comprises the following raw materials in parts by weight:
SiO217-30 parts of CaO 9-14 parts of CaCO32-4 parts of MgO and 0.4-1 part of MgO; removing SiO2The grain diameter of the other aggregates is less than or equal to 0.074 mm;
wherein SiO is2The powder comprises 7-9 parts of 40-80 meshes, 4-7 parts of 80-120 meshes and 6-14 parts of more than 325 meshes; SiO 22The powder is obtained by high-temperature calcination at 573 ℃ and heat preservation for 1 hour, and the detection value of active ingredients is more than or equal to 85 percent.
5. The polymer-modified cement-based composite board as claimed in claim 1, wherein: the cement composite additive is prepared by mixing 2 parts by weight of SM type water reducing agent, 0.6 part by weight of accelerator, 2 parts by weight of thickener and 8 parts by weight of polyvinyl alcohol with molecular weight less than 130000 under the condition of water bath; the preparation method comprises the following steps:
adding deionized water accounting for 60 wt% of the total additive solution into an electromagnetic stirring pot, adding polyvinyl alcohol, an accelerator and a thickener when heating in a water bath to 45 ℃, continuously stirring for 6h +/-10 min under the condition of 400rpm, adding a water reducing agent when measuring the pH value between 3.6 and 3.8, continuously heating to 50 ℃, keeping the stirring speed unchanged, stirring for 1h +/-15 min, immediately stopping heating when measuring the pH value between 2.1 and 2.2 and the viscosity between 130 and 160 mPa.s at the test temperature of 40 ℃, and quickly cooling to obtain the cement composite additive.
6. The polymer-modified cement-based composite board as claimed in claim 1, wherein: the solid content of the prepared cement composite additive is more than or equal to 50 percent.
7. The polymer-modified cement-based composite board as claimed in claim 1, wherein: the defoaming agent is emulsified silicone oil, polyoxyethylene polyoxypropylene pentaerythritol ether or polyoxypropylene glycerol ether.
8. The method of producing a polymer-modified cement-based composite board as set forth in any one of claims 1 to 7, characterized by comprising the steps of:
1) respectively dividing the aggregates with different meshes, the cement and the inorganic aggregates into two groups, respectively extracting the aggregates into a mixer according to the formula by a bucket elevator, uniformly mixing the aggregates and the cement, and then conveying the aggregates to two storage towers for later use;
2) during production, cement and inorganic aggregate mixture is conveyed into a stirring pot through a belt conveyer, a high-molecular mixture, a cement composite additive, a part of defoaming agent and a certain mass of water are added and stirred for 20-30 min, aggregate, citrate and the rest of defoaming agent are added and stirred for 10-15 min to be uniform, and then the mixture is injected into a mold for molding;
3) and demolding the blank, naturally drying, polishing by fixed thickness, conveying to an autoclave curing box for reaction and curing, and naturally curing after curing to obtain the composite board.
9. The method of manufacturing a polymer-modified cement-based composite board as set forth in claim 8, wherein: in the step 2), the defoaming agent is dripped twice, the dripping quantity is determined according to the actual temperature, 4-5 drops are dripped when the T is less than or equal to 25 ℃, 5-6 drops are dripped when the T is less than or equal to 26 ℃ and less than or equal to 35 ℃, and 7 drops or more are dripped when the T is more than or equal to 36 ℃;
in the step 3), the blank is subjected to fixed-thickness polishing and then conveyed to an autoclaved curing chamber, steam with the steam pressure of 0.8-1 MPa and the steam temperature of 160-180 ℃ is introduced for curing for 7-8 h, and after curing is completed, the blank is cured at normal temperature for 7d, and then is packaged and delivered out of a factory; the steam is recycled and calcined SiO through a circulating water system2The heat dissipated later is obtained.
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| CN106630878A (en) * | 2016-12-29 | 2017-05-10 | 常州工程职业技术学院 | High-temperature-resistant wall material produced by utilizing waste glass particles and preparation method of wall material |
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| CN104177031A (en) * | 2014-08-31 | 2014-12-03 | 李小海 | Foam concrete building blocks and production method thereof |
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